TW201714926A - Polycarbonate resin composition and molded object of same - Google Patents

Abstract

This polycarbonate resin composition comprises: a polycarbonate resin (A) containing a polycarbonate-polyorganosiloxane copolymer (A-1) having a specific structure; a copolymer (B) that has constitutional units derived from acrylonitrile and styrene but does not have a constitutional unit derived from methyl methacrylate; and a copolymer (C) that has constitutional units derived from butadiene and methyl methacrylate, wherein the contained amount of the polyorganosiloxane block portion in the whole resin composition is 0.1-10 mass%, the total contained amount of the constitutional unit derived from acrylonitrile in the whole resin composition and the constitutional unit derived from styrene in the whole resin composition is 8-45 mass%, the contained amount of the constitutional unit derived from butadiene in the whole resin composition is 3-10 mass%, and the viscosity average molecular weight (Mv) of (A) is 20,000-25,000.

Description

Polycarbonate resin composition and molded body thereof

The present invention relates to a polycarbonate resin composition and a molded body thereof.

Polycarbonate-polyorganosiloxane polymers (hereinafter also referred to as "PC-POS") have attracted attention due to their excellent impact resistance, chemical resistance, and flame retardancy. Therefore, polycarbonate resin compositions containing PC-POS are expected to be widely used in various fields such as electrical equipment, electronic equipment, and automobiles. In particular, it is widely used in mobile phones, mobile personal computers, digital cameras, camcorders, power tools and the like, and other daily necessities.

The polycarbonate resin composition containing PC-POS described above is also studied for further improving impact resistance, flame retardancy, and other properties such as fluidity. For example, Patent Documents 1 and 2 disclose thermoplastic resins each containing a specific amount of a polycarbonate resin, an acrylonitrile-styrene copolymer (hereinafter also referred to as "AS") or acrylonitrile-butadiene-benzene. An ethylene copolymer (hereinafter also referred to as "ABS"), a polyoxyalkylene-polycarbonate copolymer, and a phosphorus-containing flame retardant do not substantially deteriorate the impact strength, thereby improving fluidity or flame retardancy.

In the polycarbonate resin compositions which maintain the excellent flame retardancy and satisfy the moldability, the impact resistance, and the rigidity, and can form a molded article excellent in thermal stability, the polycarbonate resin composition is disclosed. A polycarbonate resin composition such as a resin, a styrene resin, and a polycarbonate-polyorganosiloxane copolymer and/or a functional group-containing polyoxonium compound.

Further, Patent Document 5 discloses a polycarbonate resin composition comprising a poly Carbonate and/or copolyestercarbonate having an aliphatic moiety, ABS resin and/or AS (acrylonitrile-styrene) resin, phosphate compound, and polyoxyalkylene-polycarbonate block copolymer And even if it is formed thin, it has excellent flame retardancy.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-52401

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-516013

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2000-191898

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2001-55500

[Patent Document 5] Japanese Patent Laid-Open No. Hei 4-285655

The polycarbonate resin composition capable of forming a thin-walled and large-sized molded body requires a high fluidity of the ABS resin grade. However, if the fluidity of the polycarbonate resin composition containing PC-POS is to be improved, the impact strength tends to be lowered, and it is difficult to achieve both fluidity and impact strength at a higher level.

Further, when an ABS resin or an AS resin or the like is added in order to improve the fluidity or impact resistance of the polycarbonate resin composition, there is a problem that flame retardancy and chemical resistance are lowered.

The problem to be solved by the present invention is to provide a polycarbonate resin composition which is excellent in fluidity, flame retardancy, and chemical resistance and which can obtain a molded body having high impact strength.

The inventors of the present invention have diligently studied and found that in the polycarbonate resin composition comprising PC-POS and a specific copolymer, by the content of the POS block portion in the resin composition and in the copolymer The content of the copolymerization component is set to a specific range, which can be solved. The above problems have thus completed the present invention.

That is, the present invention relates to the following [1] to [16].

[1] A polycarbonate resin composition comprising: a polycarbonate resin (A) comprising a polycarbonate-polyorganosiloxane copolymer (A-1), which is a polyorganosiloxane The alkane copolymer (A-1) has a polycarbonate block comprising a repeating unit represented by the following formula (I) and a polyorganosiloxane block comprising a repeating unit represented by the following formula (II) a copolymer (B) having structural units derived from acrylonitrile and styrene and having no structural unit derived from methyl methacrylate; and a copolymer (C) having a derived from butadiene and methyl a structural unit of methyl acrylate; and the content of the above polyorganosiloxane block portion in the total resin composition is 0.1 to 10% by mass, and the above-mentioned acrylonitrile-derived structural unit and total resin combination in the total resin composition The content of the above-mentioned styrene-derived structural unit is 8 to 45% by mass in total, and the content of the above-mentioned butadiene-derived structural unit in the total resin composition is 3 to 10% by mass, and the above polycarbonate The viscosity average molecular weight (Mv) of the resin (A) is 20,000 to 25,000.

[wherein R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; and X represents a single bond, an alkylene group having 1 to 8 carbon atoms, Alkylene having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a fluorenyldiyl group, an arylalkyl group having 7 to 15 carbon atoms, and a carbon number of 7 ~15 arylalkylene, -S-, -SO-, -SO ₂ -, -O- or -CO-; R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms; a and b each independently represent an integer of 0 to 4]

[2] The polycarbonate resin composition according to the above [1], wherein the content of the polyorganosiloxane component in the polycarbonate resin (A) is 0.1 to 15% by mass.

[3] The polycarbonate resin composition according to the above [1] or [2], wherein the chain length of the polyorganosiloxane block in the polycarbonate-polyorganosiloxane copolymer (A-1) It is 30~500.

[4] The polycarbonate resin composition according to any one of [1] to [3] wherein the copolymer (B) comprises an acrylonitrile-butadiene-styrene terpolymer (B- 1).

[5] The polycarbonate resin composition according to any one of [1] to [4] wherein the copolymer (B) comprises an acrylonitrile-styrene binary copolymer (B-2).

[6] The polycarbonate resin composition according to any one of [1] to [5] wherein the copolymer (C) comprises a ternary selected from methyl methacrylate-butadiene-styrene. At least one of a group consisting of a copolymer and a methyl methacrylate-butadiene binary copolymer.

[7] The polycarbonate resin composition according to any one of [1] to [6] wherein the copolymer (C) is a methyl methacrylate-butadiene binary copolymer.

[8] The polycarbonate resin composition according to any one of [1] to [7] wherein the copolymer (C) has an average particle diameter of from 100 nm to 300 nm.

[9] The polycarbonate resin composition according to any one of the above [5], wherein the acrylonitrile-butadiene-benzene is the above-mentioned 100 parts by mass of the polycarbonate resin (A). The content of the ethylene terpolymer (B-1) is 8 to 100 parts by mass, the content of the acrylonitrile-styrene binary copolymer (B-2) is 20 parts by mass or less, and the copolymer (C) is The content is 1 to 8 parts by mass.

[10] The polycarbonate resin composition according to any one of [1] to [9] further comprising a flame retardant (D).

[11] The polycarbonate resin composition according to [10] above, wherein the component (D) It is a phosphorus-based flame retardant.

[12] The polycarbonate resin composition according to [11], wherein the phosphorus-based flame retardant is a condensed phosphate.

[13] The polycarbonate resin composition according to any one of the above [10], wherein the content of the flame retardant (D) is 100 parts by mass based on the polycarbonate resin (A). It is 10 to 40 parts by mass.

[14] A polycarbonate resin composition comprising: a polycarbonate resin (A) comprising a polycarbonate-polyorganosiloxane copolymer (A-1), the polycarbonate-polyorganooxime The alkane copolymer (A-1) has a polycarbonate block comprising a repeating unit represented by the following formula (I) and a polyorganosiloxane block comprising a repeating unit represented by the following formula (II) Copolymer (B) having structural units derived from acrylonitrile and styrene and having no structural unit derived from methyl methacrylate; copolymer (C) having derived from butadiene and methacrylic acid a structural unit of a methyl ester; and a flame retardant (D); and the copolymer (C) is a methyl methacrylate-butadiene binary copolymer, and the flame retardant (D) is a phosphorus as a condensed phosphate Is a flame retardant, and the content of the above polyorganosiloxane block portion in the total resin composition is 0.1 to 10% by mass, and the above-mentioned acrylonitrile-derived structural unit and total resin composition in the total resin composition The total content of the above-mentioned structural unit derived from styrene is 8 to 45% by mass, and the above-mentioned structural unit derived from butadiene in the total resin composition Content is 3 to 10% by mass, and the polycarbonate resin (A) of the viscosity average molecular weight (Mv) of 20,000 to 25,000.

[wherein R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; and X represents a single bond, an alkylene group having 1 to 8 carbon atoms, Alkylene having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a fluorenyldiyl group, an arylalkyl group having 7 to 15 carbon atoms, and a carbon number of 7 ~15 arylalkylene, -S-, -SO-, -SO ₂ -, -O- or -CO-; R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms; a and b each independently represent an integer of 0 to 4]

[15] The polycarbonate resin composition according to the above [14], wherein the copolymer (B) is contained in an amount of from 8 to 100 parts by mass based on 100 parts by mass of the polycarbonate resin (A), and the copolymerization is carried out. The content of the substance (C) is 1 to 8 parts by mass, and the content of the flame retardant (D) is 10 to 40 parts by mass.

[16] A molded article comprising the polycarbonate resin composition according to any one of the above [1] to [15].

According to the present invention, it is possible to provide a polycarbonate resin composition which is excellent in fluidity, flame retardancy and chemical resistance and which can obtain a molded body having high impact strength.

Hereinafter, the polycarbonate resin composition of the present invention will be described in detail. Furthermore, in the present specification, the regulations regarded as being preferable can be arbitrarily employed, and it is considered that the preferred combinations are better. In addition, in this specification, the description of "XX~YY" means "XX or more and YY or less."

[Polycarbonate Resin Composition]

The polycarbonate resin composition of the present invention is characterized by comprising: a polycarbonate resin (A) comprising a polycarbonate-polyorganosiloxane copolymer (A-1), which has a polycarbonate-poly The oxime copolymer (A-1) has a polycarbonate block comprising a repeating unit represented by the following formula (I) and a polyorgano oxime comprising a repeating unit represented by the following formula (II) An alkane block; a copolymer (B) having a structural unit derived from acrylonitrile and styrene and having no structural unit derived from methyl methacrylate; and a copolymer (C) having a derived from butadiene And a structural unit of methyl methacrylate; and the content of the above polyorganosiloxane block portion in the total resin composition is 0.1 to 10% by mass, and the above-mentioned structural unit derived from acrylonitrile in the total resin composition The total content of the above-mentioned styrene-derived structural unit in the total resin composition is from 8 to 45% by mass, and the content of the above-mentioned butadiene-derived structural unit in the total resin composition is from 3 to 10% by mass, and The polycarbonate resin (A) has a viscosity average molecular weight (Mv) of 20,000 to 25,000.

[wherein R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; and X represents a single bond, an alkylene group having 1 to 8 carbon atoms, Alkylene having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a fluorenyldiyl group, an arylalkyl group having 7 to 15 carbon atoms, and a carbon number of 7 ~15 arylalkylene, -S-, -SO-, -SO ₂ -, -O- or -CO-; R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms; a and b each independently represent an integer of 0 to 4]

[Polycarbonate Resin (A)]

The polycarbonate resin (A) used in the present invention (hereinafter also referred to as "(A) component") It is characterized by containing a polycarbonate-polyorganosiloxane copolymer (A-1) (hereinafter also referred to as "PC-POS (A-1)" or "(A-1) component). In addition, as the component (A), the aromatic polycarbonate resin (A-2) other than the component (A-1) may be contained to the extent that the effects of the present invention are not impaired.

The content of the polyorganosiloxane block portion containing the repeating unit represented by the formula (II) in the polycarbonate resin (A) is preferably from 0.1 to 15% by mass, more preferably from 0.25 to 10% by mass, further It is preferably 0.4 to 6.0% by mass. When the content is 0.1% by mass or more, the effect of improving the impact strength is higher, and when it is 15% by mass or less, it is easy to avoid a decrease in impact strength.

Here, the content of the above polyorganosiloxane block portion in the component (A) can be calculated by nuclear magnetic resonance (NMR).

The polycarbonate resin (A) has a viscosity average molecular weight (Mv) of 20,000 to 25,000, preferably 21,000 to 24,000, and more preferably 22,000 to 23,000. When the viscosity average molecular weight of the component (A) is in this range, the balance between fluidity and impact resistance is more excellent.

Further, in the present invention, the viscosity average molecular weight (Mv) is determined by a Ubbelohs viscosity tube to determine the ultimate viscosity [η] of a dichloromethane solution (concentration unit: g/L) at 20 ° C, and according to Schnell's formula ([η]=1.23×10 ^-5 ×Mv ^0.83 ) and the calculated value.

With respect to the content of the component (A-1) in the component (A), the content of the polyorganosiloxane component in the component (A) is preferably adjusted to the above range, and is preferably 10 ~100% by mass, more preferably 15 to 100% by mass, still more preferably 20 to 100% by mass.

When the component (A-1) is 10% by mass or more, it is not necessary to increase the content of the polyorganosiloxane block portion in the component (A-1), which is preferable in the production of PC-POS.

<Polycarbonate-polyorganosiloxane copolymer (A-1)>

PC-POS (A-1) has a polycarbonate block comprising a repeating unit represented by the following formula (I) and a polyorganooxylane inclusion comprising a repeating unit represented by the following formula (II); Segment of polycarbonate-polyorganosiloxane copolymer.

[wherein R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; and X represents a single bond, an alkylene group having 1 to 8 carbon atoms, Alkylene having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a fluorenyldiyl group, an arylalkyl group having 7 to 15 carbon atoms, and a carbon number of 7 ~15 arylalkylene, -S-, -SO-, -SO ₂ -, -O- or -CO-; R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms; a and b each independently represent an integer of 0 to 4]

One type of PC-POS (A-1) may be used alone or two or more types may be used in combination. Further, the type of the repeating unit represented by the formula (I) in PC-POS (A-1) may be one type or two or more types. The same applies to the repeating unit represented by the formula (II) in PC-POS (A-1).

In the above formula (I), examples of the halogen atom independently represented by R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group independently represented by R ¹ and R ² include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and various butyl groups (so-called "various", and those which include a linear chain and all branches are included. , the same as below), various pentyl groups, various hexyl groups. Examples of the alkoxy group in which R ¹ and R ² are each independently represent a case where the alkyl group is the above alkyl group.

R ¹ and R ² are each preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

The alkylene group represented by X may, for example, be a methylene group, an ethylidene group, a trimethylene group, a tetramethylene group or a hexamethylene group, and is preferably an alkylene group having 1 to 5 carbon atoms. As a table of X Examples of the alkylene group include an ethylene group and an isopropylidene group. The cycloalkyl group represented by X is preferably a cycloalkyl group having 5 to 10 carbon atoms, and examples thereof include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group. Examples of the cycloalkylene group represented by X include a cyclohexylene group, a 3,5,5-trimethylcyclohexylene group, a 2-adamantyl group, and the like, and preferably a cycloalkane having a carbon number of 5 to 10. The base is more preferably a cycloalkylene group having 5 to 8 carbon atoms. The aryl group of the arylalkyl group represented by X may, for example, be an aryl group having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group or a fluorenyl group. The aryl group of the arylalkylene group represented by X may, for example, be an aryl group having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group or a fluorenyl group.

a and b each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1.

In the general formula (II), examples of the halogen atom independently represented by R ³ and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group and the alkoxy group which are independently represented by R ³ and R ⁴ include the same as those in the case of R ¹ and R ² . Examples of the aryl group independently represented by R ³ and R ⁴ include a phenyl group and a naphthyl group.

Further, R ³ and R ⁴ are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably both. Is a methyl group.

The chain length of the polyorganooxyalkylene block in PC-POS (A-1) is preferably from 30 to 500, more preferably from 30 to 150, still more preferably from 30 to 120. When the chain length of the polyorganosiloxane mixture in PC-POS (A-1) is 30 or more, the impact resistance is sufficient. When the chain length of the polyorganosiloxane mixture in PC-POS (A-1) is 500 or less, the workability in producing a copolymer is good.

The structure of the polyorganosiloxane mixture containing the repeating unit represented by the formula (II) is preferably represented by the following formula (II-I) to (II-III).

[wherein R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and plural R ³ ~ R ⁶ may be mutually the same or different from; the Y represents ^{-R 7 O -, - R 7} COO -, - R 7 NH -, - R 7 NR 8 -, - COO -, - S -, - R 7 COO-R ⁹ -O-, or -R ⁷ OR ¹⁰ -O-, plural Y may be the same or different; R ⁷ represents a single bond, a linear, a branched or a cyclic alkyl group, an aryl group Substituted alkyl, substituted or unsubstituted aryl, or di extended aryl; R ⁸ represents alkyl, alkenyl, aryl, or aralkyl; R ⁹ represents diaryl; R ¹⁰ represents a linear, branched or cyclic alkylene group or a di extended aryl group; β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a halide of a dicarboxylic acid or a dicarboxylic acid; n represents The average chain length of the polyorganosiloxane; p and q are each an integer of 1 or more, and the sum of p and q is n-2]

Examples of the halogen atom independently represented by R ³ to R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group independently represented by R ³ to R ⁶ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. Examples of the alkoxy group each independently represented by R ³ to R ⁶ include the case where the alkyl group is the above alkyl group. Examples of the aryl group independently represented by R ³ to R ⁶ include a phenyl group and a naphthyl group.

R ³ to R ⁶ are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.

R ³ to R ⁶ in the general formulae (II-I), (II-II) and/or (II-III) are preferably all methyl groups.

Represented by Y of ^{-R 7 O -, - R 7} COO -, - R 7 NH -, - R 7 NR 8 -, - COO -, - S -, - R 7 COO-R 9 -O-, or The linear or branched alkyl group represented by R ⁷ in -R ⁷ OR ¹⁰ -O- may, for example, be an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, as a cyclic alkylene group. The base may, for example, be a cycloalkyl group having 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms.

The content of the polyorganosiloxane mixture block portion containing the repeating unit represented by the general formula (II) in PC-POS (A-1) is preferably 2.0 to 15% by mass, more preferably 3.0 to 8.5% by mass, Further, it is preferably 3.2 to 7.5% by mass. When the content is 2.0% by mass or more, the impact resistance of the obtained resin composition is further improved. Moreover, when it is 15 mass% or less, the handleability at the time of manufacture of PC-POS (A-1) is more favorable.

The viscosity average molecular weight (Mv) of PC-POS (A-1) is preferably from 10,000 to 25,000, more preferably from 12,000 to 23,000. When the viscosity average molecular weight of the component (A-1) is within this range, the balance between fluidity and impact resistance is easily obtained.

In order to have such a characteristic as the polyorganosiloxane mixture constituting the PC-POS (A-1) used in the present invention, the following formula (1), (2) and/or (3) can be used. Polyorganosiloxane is used as a raw material.

[wherein R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and plural R ³ ~ R ⁶ may be mutually the same or different from; the Y represents ^{-R 7 O -, - R 7} COO -, - R 7 NH -, - R 7 NR 8 -, - COO -, - S -, - R 7 COO-R ⁹ -O-, or -R ⁷ OR ¹⁰ -O-, plural Y may be the same or different; R ⁷ represents a single bond, a linear, a branched or a cyclic alkyl group, an aryl group Substituted alkyl, substituted or unsubstituted aryl, or di extended aryl; R ⁸ represents alkyl, alkenyl, aryl or aralkyl; R ⁹ represents diaryl; R ¹⁰ represents a linear, branched or cyclic alkyl group, or a di extended aryl group; Z represents a hydrogen atom or a halogen atom, and a plurality of Z may be the same or different from each other; β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a halide of a dicarboxylic acid or a dicarboxylic acid; p and q are each an integer of 1 or more, and a sum of p and q is n-2; n represents an average chain length of the polyorganosiloxane;

Examples of the halogen atom independently represented by R ³ to R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group independently represented by R ³ to R ⁶ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. Examples of the alkoxy group each independently represented by R ³ to R ⁶ include the case where the alkyl group is the above alkyl group. Examples of the aryl group independently represented by R ³ to R ⁶ include a phenyl group and a naphthyl group.

R ³ to R ⁶ are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.

As the polyorganosiloxane which is represented by the general formulae (1), (2) and/or (3), R ³ to R ⁶ are preferably each a methyl group.

Represented by Y of ^{-R 7 O -, - R 7} COO -, - R 7 NH -, - R 7 NR 8 -, - COO -, - S -, - R 7 COO-R 9 -O-, or The linear or branched alkyl group represented by R ⁷ in -R ⁷ OR ¹⁰ -O- may, for example, be an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, as a cyclic alkylene group. The base may, for example, be a cycloalkyl group having 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms.

The aryl group substituted with an alkyl group represented by R ⁷ may have a substituent such as an alkoxy group or an alkyl group in the aromatic ring, and as a specific structure thereof, for example, a structure of the following formula (4) or (5) can be exemplified. . Further, in the case of having an aryl group substituted alkyl group, the alkyl group is bonded to Si.

[where c represents a positive integer, usually an integer from 1 to 6]

The diaryl group represented by R ⁷ , R ⁹ and R ¹⁰ means a group in which two aryl groups are directly bonded or linked via a divalent organic group, specifically, -Ar ¹ -W-Ar ² - The basis of the structure represented. Here, Ar ¹ and Ar ² represent an extended aryl group, and W represents a single bond or a divalent organic group. The divalent organic group represented by W is, for example, an isopropylidene group, a methylene group, a dimethylene group or a trimethylene group.

Examples of the extended aryl group represented by R ⁷ , Ar ¹ and Ar ² include an extended aryl group having a ring carbon number of 6 to 14 such as a phenyl group, an anthranyl group, a phenylene group or a fluorene group. The aryl group may have any substituent such as an alkoxy group or an alkyl group.

The alkyl group represented by R ⁸ is a straight or branched chain having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. Examples of the alkenyl group include a linear or branched chain having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a phenylmethyl group and a phenylethyl group.

The linear, branched or cyclic alkyl group represented by R ¹⁰ is the same as R ⁷ .

Y is preferably -R ⁷ O-, and R ⁷ is an aryl-substituted alkylene group, and particularly a residue of a phenolic compound having an alkyl group, more preferably an organic residue derived from allylphenol. Or an organic residue derived from eugenol.

Further, with respect to p and q in the formula (2), p = q, that is, p = (n - 2) / 2, q = (n - 2) / 2 is preferable.

n is preferably 20 to 85, more preferably 20 to 75, and still more preferably 20 to 60, as described above.

Further, β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a halide of a dicarboxylic acid or a dicarboxylic acid, and examples thereof include the following formulas (6-1) to (6-5). Representation Divalent base.

Examples of the polyorganosiloxane which is represented by the formula (1) include the following compounds of the formulae (1-1) to (1-11).

In the above formulae (1-1) to (1-11), R ³ to R ⁶ , n and R ^{8 are} as defined above, and preferably also the same. c represents a positive integer, usually an integer from 1 to 6.

Among these, a phenol-modified polyorganosiloxane represented by the above formula (1-1) is preferred from the viewpoint of easiness of polymerization. Further, from the viewpoint of easiness of acquisition, α,ω-bis[3-(o-hydroxyphenyl)propyl]poly group which is one of the compounds represented by the above formula (1-2) is preferred. Dimethyl methoxy oxane, α, ω-bis[3-(4-hydroxy-3-methoxyphenyl) propyl] poly(ethylene) as one of the compounds represented by the above formula (1-3) Methyl decane.

Further, as the polyorganosiloxane raw material, those having the following general formula (1-12) can also be used.

[化10]

In the formula, R ³ and R ⁴ are the same as those described above. The average chain length of the polyorganosiloxane mixture represented by the formula (1-12) is (r × m), and the range of (r × m) is the same as the above n.

In the case where the above (1-12) is used as the raw material of the polyorganosiloxane, the polyorganooxyalkylene block preferably has a repeating unit represented by the following formula (II-IV).

[wherein R ³ , R ⁴ , r and m are as described above]

In addition to the above, it is also possible to preferably use Japanese Patent Laid-Open Publication No. 2013-523938, Japanese Patent Laid-Open No. Hei-4-225059, Japanese Patent Publication No. 2006-518803, and International Publication No. 2013/115604 A polyorganosiloxane compound as described in No.

The gel permeation chromatography (GPC) device for obtaining the measurement value of the molecular weight and molecular weight distribution of the polyorganosiloxane is not particularly limited, and a commercially available GPC device such as a refractive index manufactured by Tosoh Co., Ltd. can be used. (RI) built-in GPC measuring machine "HLC-8200". Specifically, as the GPC column, "TSK-GEL G4000HXL" and "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd. were used. The column temperature was set to 40 ° C, and the eluent was measured using tetrahydrofuran (THF) at a flow rate of 1.0 mL/min.

The method for producing the polyorganosiloxane is not particularly limited. For example, a cyclotrioxane and a dioxane are reacted in the presence of an acid catalyst to synthesize α,ω-dihydroorganopentaoxane, and then, according to the method described in JP-A-H11-217390, Yu Yu a phenolic compound (for example, 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.) and the like, and the α,ω-dihydroorganic five in the presence of a catalyst for hydrogenation reaction The oxirane is subjected to an addition reaction, whereby a crude polyorganosiloxane can be obtained. Further, according to the method described in Japanese Patent No. 2662310, octamethylcyclotetraoxane and tetramethyldioxane are reacted in the presence of sulfuric acid (acid catalyst) to obtain α. The ω-dihydropolyorganosiloxane is subjected to an addition reaction with a phenolic compound or the like in the presence of a catalyst for hydrogenation reaction in the same manner as described above, whereby a crude polyorganosiloxane can be obtained. Further, the α,ω-dihydropolyorganosiloxane may be used by appropriately adjusting the chain length n depending on the polymerization conditions, and a commercially available α,ω-dihydropolyorganosiloxane may also be used.

The catalyst for the hydrogenation reaction of the above-mentioned hydrazine is a transition metal-based catalyst. Among them, a platinum-based catalyst is preferably used in terms of reaction rate and selectivity. Specific examples of the platinum-based catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, a complex of platinum and a vinylidene-containing alkane, and a platinum-supported cerium oxide. , carrying platinum activated carbon and the like.

Preferably, the transition metal of the transition metal catalyst used as the catalyst for the above hydrogenation reaction is contained in the crude polyorganosiloxane by contacting the crude polyorganosiloxane with the adsorbent. It is removed by adsorption to an adsorbent.

As the adsorbent, for example, those having an average pore diameter of 1000 Å or less can be used. If the average pore diameter is 1000 Å or less, the transition metal in the crude polyorganosiloxane can be efficiently removed. From this point of view, the average pore diameter of the adsorbent is preferably 500 Å or less, more preferably 200 Å or less, further preferably 150 Å or less, and further preferably 100 Å or less. Further, from the same viewpoint, the adsorbent is preferably a porous adsorbent.

The adsorbent is not particularly limited as long as it has the above average pore diameter. For example, activated clay, acid clay, activated carbon, synthetic zeolite, natural zeolite, activated alumina, ceria, cerium oxide-magnesia can be used. An adsorbent, diatomaceous earth, cellulose, etc., preferably selected from the group consisting of activated clay, acid clay, activated carbon, synthetic zeolite, At least one of a group consisting of natural zeolite, activated alumina, ceria, and ceria-magnesia-based adsorbent.

After adsorbing the transition metal contained in the crude polyorganosiloxane to the adsorbent, the adsorbent can be separated from the polyorganosiloxane by any separation means. As means for separating the adsorbent from the polyorganosiloxane, for example, a filter or centrifugal separation can be mentioned. In the case of using a filter, a filter such as a membrane filter, a sintered metal filter, or a glass fiber filter can be used, and a membrane filter is particularly preferably used.

After adsorbing the transition metal, the average particle diameter of the adsorbent is usually from 1 μm to 4 mm, preferably from 1 to 100 μm, from the viewpoint of separating the adsorbent from the polyorganosiloxane.

In the case of using the above adsorbent, the amount thereof to be used is not particularly limited. The porous adsorbent may be used in an amount of from 1 to 30 parts by mass, more preferably from 2 to 20 parts by mass, per 100 parts by mass of the crude polyorganosiloxane.

Furthermore, when the crude polyorganosiloxane to be treated has a high molecular weight and is not in a liquid state, it may be heated to, for example, a polyorganosiloxane when the adsorption by the adsorbent and the separation of the adsorbent are carried out. The temperature at which it becomes a liquid state. Alternatively, it may be dissolved in a solvent such as dichloromethane or hexane.

"Manufacturing Method of PC-POS (A-1)"

As a method of producing the PC-POS (A-1) used in the present invention, a known production method such as an interfacial polymerization method (phosgene method), a pyridine method, or a transesterification method can be used. Especially in the case of the interfacial polymerization method, the separation step of the organic phase containing PC-POS (A-1) and the aqueous phase containing unreacted materials or catalyst residues becomes easy, using alkali cleaning, acid cleaning, and pure The separation of the organic phase and the aqueous phase containing PC-POS (A-1) in each washing step of the water washing becomes easy, and PC-POS (A-1) can be obtained with high efficiency.

The production method of the PC-POS (A-1) is not particularly limited, and it can be produced by a method described in the known PC-POS, for example, the method described in JP-A-2010-241943.

Specifically, it can be produced by dissolving a previously produced polycarbonate oligomer and the above polyorganosiloxane in a water-insoluble organic solvent (dichloromethane or the like), and adding a dihydric phenol system. An aqueous solution of a basic compound (such as an aqueous sodium hydroxide solution) of a compound (such as bisphenol A), using a tertiary amine (triethylamine or the like) or a quaternary ammonium salt (trimethylbenzylammonium chloride or the like) as a polymerization catalyst The interfacial polycondensation reaction is carried out in the presence of a terminal blocking agent (monohydric phenol such as tributylphenol). Further, PC-POS (A-1) can also be produced by copolymerizing a polyorganosiloxane, a dihydric phenol, and a phosgene, a carbonate or a chloroformate.

The polycarbonate oligomer can be produced by reacting a dihydric phenol with a carbonate precursor such as phosgene or triphosgene in an organic solvent such as dichloromethane, chlorobenzene or chloroform. Further, when a polycarbonate oligomer is produced by a transesterification method, it can also be produced by a reaction of a dihydric phenol with a carbonate precursor such as diphenyl carbonate.

As the dihydric phenol, a dihydric phenol represented by the following formula (i) is preferably used.

In the formula, R ¹ , R ² , a, b and X are as described above.

Examples of the dihydric phenol represented by the above formula (i) include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyarylethers, and dihydroxydiarylsulfides. Ethers, dihydroxydiaryl sulfoxides, dihydroxydiaryl fluorenes, dihydroxybiphenyls, dihydroxydiaryl fluorenes, dihydroxy diol arylcycloalkanes, and the like. These dihydric phenols may be used alone or in combination of two or more.

Examples of the bis(hydroxyaryl)alkane include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxyphenyl). ) propane [bisphenol A], 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, Bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4- Hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2 - bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5 -Dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and the like.

Examples of the bis(hydroxyaryl)cycloalkane include 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1. - bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl) Alkane, 1,1-bis(4-hydroxyphenyl)cyclododecane, and the like. Examples of the dihydroxyaryl ethers include 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether.

Examples of the dihydroxydiaryl sulfides include 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide. Examples of the dihydroxydiarylhydrazines include 4,4'-dihydroxydiphenylarylene and 4,4'-dihydroxy-3,3'-dimethyldiphenylarylene. Examples of the dihydroxydiarylfluorenes include 4,4'-dihydroxydiphenylfluorene and 4,4'-dihydroxy-3,3'-dimethyldiphenylphosphonium.

Examples of the dihydroxybiphenyls include 4,4'-dihydroxybiphenyl. Examples of the dihydroxydiarylfluorenes include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and the like. Examples of the dihydroxydiaryladamantane include 1,3-bis(4-hydroxyphenyl)adamantane, 2,2-bis(4-hydroxyphenyl)adamantane, and 1,3-double ( 4-hydroxyphenyl)-5,7-dimethyl adamantane and the like.

Examples of the dihydric phenol other than the above include 4,4'-[1,3-phenylphenylbis(1-methylethylidene)]bisphenol and 10,10-bis(4-hydroxyphenyl). -9-fluorenone, 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentane, and the like.

These dihydric phenols may be used alone or in combination of two or more.

Among these, a bis(hydroxyphenyl)alkane is preferred, and bisphenol A is more preferred. In the case where bisphenol A is used as the dihydric phenol, in the above formula (i), X is an isopropylidene group, and a = b = 0.

In order to adjust the molecular weight of the obtained PC-POS, a terminal blocking agent can be used. Examples of the terminal blocking agent include phenol, p-cresol, p-tert-butylphenol, p-t-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol, and A monohydric phenol such as a third amyl phenol. These monohydric phenols may be used alone or in combination of two or more.

After the above-mentioned interfacial polycondensation reaction, it is allowed to stand still and separate into an aqueous phase and an organic solvent phase [separation step], and the organic solvent phase is washed (preferably, sequentially washed with an alkaline aqueous solution, an acidic aqueous solution, or water). Step], the obtained organic phase is concentrated [concentration step] and dried [drying step], whereby a PC-POS copolymer can be obtained.

The above phenol-modified polyorganosiloxane can be produced by a known method. As a manufacturing method, the method shown below is mentioned, for example.

First, a cyclo-trioxane and a dioxane are reacted in the presence of an acidic catalyst to synthesize an α,ω-dihydropolyorganosiloxane. At this time, by changing the addition ratio of the cyclotrioxane to the dioxane, an α,ω-dihydropolyorganosiloxane having a desired average chain length can be synthesized. Then, in the presence of a catalyst for hydrogenation reaction, a phenol compound having an unsaturated aliphatic hydrocarbon group such as allylphenol or eugenol is subjected to an addition reaction with the α,ω-dihydropolyorganosiloxane. This makes it possible to produce a phenol-modified polyorganosiloxane having the desired average chain length.

Further, at this stage, the low molecular weight cyclic polyorganosiloxane or the excess of the phenol compound remains as impurities, and therefore it is preferred to heat under reduced pressure to distill off the low molecular compound.

<Aromatic polycarbonate resin (A-2)>

As described above, as the component (A), the aromatic polycarbonate resin (A-2) other than the component (A-1) may be contained to the extent that the effects of the present invention are not impaired (hereinafter also referred to as "(A-2)" )ingredient"). The component (A-2) is obtained by using an aromatic dihydric phenol-based compound, and can be used for adjusting the polyorganooxynonane block portion containing the repeating unit represented by the general formula (II) contained in the component (A). content.

The viscosity average molecular weight (Mv) of the aromatic polycarbonate resin of the component (A-2) is preferably from 10,000 to 40,000, more preferably from 13,000 to 30,000, from the viewpoint of the physical property.

The aromatic polycarbonate resin (A-2) is not a repeating structure represented by the above formula (II), and preferably contains a repeating unit represented by the following formula (III) as a main chain. As such an aromatic polycarbonate resin, various known aromatic polycarbonate resins can be used without particular limitation.

Wherein R ⁹ and R ¹⁰ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; and X' represents a single bond and an alkylene group having 1 to 8 carbon atoms; , an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, -S-, -SO-, -SO ₂ -, -O- or -CO-;d and e independently represent integers from 0 to 4]

Specific examples of R ⁹ and R ¹⁰ include the same as those of R ¹ and R ² described above, and preferred ones are also the same. R ⁹ and R ^{10 are more} preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Specific examples of X' include the same as those of X described above, and preferred ones are also the same. d and e are each independently preferably 0 to 2, more preferably 0 or 1.

Specifically, the above aromatic polycarbonate resin can be obtained by using a method in which an aromatic dihydric phenol compound and an aromatic dihydric phenol compound are obtained in the presence of an organic solvent inert to the reaction or an aqueous alkaline solution. After the phosgene is reacted, an interfacial polymerization method in which a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added is carried out; or an aromatic dihydric phenol compound is dissolved in a mixed solution of pyridine or pyridine and an inert solvent, and light is introduced. A method for producing a prior aromatic polycarbonate such as a pyridine method which is directly produced by gas.

In the above reaction, a molecular weight modifier (terminal blocking agent), a branching agent, or the like is used as needed.

In addition, examples of the aromatic dihydric phenol compound include those represented by the following formula (III').

Wherein R ⁹ , R ¹⁰ , X', d and e are as defined above, and preferably the same]

Specific examples of the aromatic dihydric phenol compound include 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, and 1,1- Bis(4-hydroxyphenyl)ethane, bis(hydroxyphenyl)alkane such as 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxyl linkage Benzene, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)anthracene, bis(4-hydroxyl) Phenyl) anthracene, bis(4-hydroxyphenyl) ketone, and the like.

Among these, a bis(hydroxyphenyl)alkane-based dihydric phenol is preferred, and bisphenol A is more preferred.

The above-mentioned aromatic polycarbonate resin (A-2) may be used alone or in combination of two or more.

[Copolymer (B)]

The polycarbonate resin composition of the present invention contains, as the component (B), a copolymer having a structural unit derived from acrylonitrile and styrene and having no structural unit derived from methyl methacrylate. When the component (B) is contained in the polycarbonate resin composition, a resin composition which is excellent in fluidity and which has good compatibility with the component (A) due to a structural unit derived from acrylonitrile can be obtained.

Examples of the component (B) include an acrylonitrile-styrene binary copolymer (AS) and a copolymer of three or more elements obtained by further copolymerizing acrylonitrile and styrene with other components. Wait.

Specific examples of the other components include polybutadiene, (meth) acrylate (excluding methyl methacrylate), styrene-butadiene-styrene rubber (SBS), and styrene-butyl. Diene rubber (SBR), butadiene-acrylic rubber, isoprene rubber, isoprene-styrene rubber, isoprene-acrylic rubber, ethylene-propylene rubber, ethylene-propylene-diene Rubber, etc. Among them, the most preferred one is polybutadiene. As the polybutadiene used herein, a low cis polybutadiene (for example, a 1 to 30 mol% containing a 1,2-vinyl bond and a 30 to 42 mol% of a 1,4-cis bond) may be used. Any of high cis-type polybutadiene (for example, containing 20 mol% or less of a 1,2-vinyl bond and 78 mol% or more of a 1,4-cis bond) may be such a mixture.

Specific examples of the above trivalent or higher copolymer include an acrylonitrile-acrylate-styrene terpolymer (AAS), and an acrylonitrile-butyl group obtained by polymerizing acrylonitrile and styrene with polybutadiene. Diene-styrene terpolymer (ABS), acrylonitrile-(ethylene/propylene/diene copolymer)-styrene copolymer (AES), and the like.

These copolymers may be used alone or in combination of two or more.

In the above copolymer, in order to improve fluidity and to improve impact resistance by containing a rubber component, it is preferred that the component (B) contains at least an acrylonitrile-butadiene-styrene terpolymer (B). -1) (hereinafter also referred to as "(B-1) component"). Further, in terms of improving the fluidity, the acrylonitrile-styrene binary copolymer (B-2) (hereinafter also referred to as "(B-2) component") may be further included.

The content of the butadiene-derived structural unit in the component (B-1) is preferably from 8 to 75% by mass, more preferably from 8 to 50% by mass, still more preferably from 8 to 25% by mass. When the content of the structural unit derived from butadiene in the component (B-1) is 8% by mass or more, the impact resistance of the molded body is further improved.

The melt volume rate (MVR) of the component (B-2) measured at a temperature of 200 ° C and a load of 10 kgf is preferably from 3 to 150 cm ³ / 10 minutes. When the MVR of the component (B-2) is in the above range, the fluidity of the resin composition is further improved. In particular, when the content of the structural unit derived from butadiene is 30 to 70% by mass as the component (B-1), the component (B-2) used for the purpose of improving fluidity is used. The above MVR is preferably 50 to 150 cm ³ /10 minutes.

The MVR can be measured by the method according to ISO 1133.

For the commercial products of the ABS as the component (B-1), "Santac AT-05", "Kralastic SXH-330" (above, manufactured by A&L Co., Ltd., Japan), "Toyolac 500", "Toyolac" 700" (above is manufactured by Toray Co., Ltd.), "PA-756" (manufactured by Chi Mei Industrial Co., Ltd.), "HR181" (manufactured by KUMHO PETROCHEMICAL Co., Ltd.), etc. In addition, as for the commercial item of AS as the component (B-2), "290FF" (manufactured by Techno Polymer Co., Ltd.), "S100N", "S200N", and "S101N" (the above are UMG ABS shares) Manufactured by the company, "PN-117C" (manufactured by Chi Mei Industrial Co., Ltd.).

[Copolymer (C)]

The polycarbonate resin composition of the present invention contains a copolymer having a structural unit derived from butadiene and methyl methacrylate as the component (C). By containing the component (C), a resin composition which is particularly excellent in impact resistance can be obtained.

Examples of the component (C) include methyl methacrylate-butadiene-styrene terpolymer (MBS) and methyl group obtained by polymerizing methyl methacrylate and styrene with polybutadiene. Methyl acrylate-acrylonitrile-butadiene-styrene tetrapolymer (MABS), methyl methacrylate-butadiene binary copolymer (MB), and the like.

These copolymers may be used alone or in combination of two or more. Among them, in terms of improving impact resistance, the component (C) preferably comprises a binary selected from the group consisting of methyl methacrylate-butadiene-styrene terpolymer and methyl methacrylate-butadiene. At least one of the groups consisting of the copolymers more preferably comprises a methyl methacrylate-butadiene binary copolymer.

The average particle diameter of the component (C) is preferably from 100 to 300 nm, more preferably from 125 to 275 nm, still more preferably from 150 to 250 nm. When the particle diameter of the component (C) is 100 nm or more and 300 nm or less, a polycarbonate resin composition having higher impact resistance can be obtained.

The method for measuring the average particle diameter of the component (C) is measured by a transmission electron microscope. Specifically, a 2 mm thick flat plate obtained by melt-kneading (A-2) component/(C) component=mass ratio 95/5 is obtained by observing a transmission electron microscope. The photograph is calculated as the average of the number of diameters of 100 particles.

As a commercial item of the MBS, "Metablen C223A" (manufactured by Mitsubishi Rayon Co., Ltd.), "Denka TH Polymer" (manufactured by Electric Chemical Industry Co., Ltd.), "Kaneace B" (manufactured by Kaneka Co., Ltd.), "Paraloid EXL2620" (manufactured by Dow Chemical). As a commercial item of MABS, "Denka CL Polymer", "Denka TE Polymer", "Denka TP Polymer" (The above is manufactured by Electric Chemical Industry Co., Ltd.), etc. are mentioned. As a commercial item of MB, "Kaneace M-711" (made by Kaneka Co., Ltd.), "Paraloid EXL2603", "Paraloid EXL2690" (above, manufactured by Dow Chemical), etc. are mentioned.

Here, in the polycarbonate resin composition of the present invention, (B) component ((B-1) component, (B-2) component), and (C) component with respect to 100 mass parts of (A) component. The preferred content is as follows. When the content of each component is in the following range, the balance between fluidity and impact resistance is further improved.

The polycarbonate resin composition of the present invention preferably has a content of the component (B) of 8 to 100 parts by mass and a content of the component (C) of 1 to 8 parts by mass based on 100 parts by mass of the component (A). . More preferably, the content of the component (B) is 8 to 70 parts by mass, and the content of the component (C) is 1 to 6 parts by mass.

The polycarbonate resin composition of the present invention preferably has a content of (B-1) component of 8 to 100 parts by mass and a content of (B-2) component of 20 parts by mass based on 100 parts by mass of the component (A). The content of the following components and (C) is 1 to 8 parts by mass. More preferably, the content of the component (B-1) is 8 The content of the component (B-2) is from 1 to 20 parts by mass, and the content of the component (C) is from 1 to 6 parts by mass. In the case where the content of the butadiene-derived structural unit of the component (B-1) is from 30 to 70% by mass, the content is preferably (B-1) based on 100 parts by mass of the component (A). The content of the component is 8 to 15 parts by mass, the content of the component (B-2) is 10 to 25 parts by mass, and the content of the component (C) is 1 to 6 parts by mass.

In the polycarbonate resin composition of the present invention, the polyorganosiloxane block portion containing the repeating unit represented by the formula (II) is contained in an amount of 0.1 to 10% by mass based on the total resin composition, preferably 0.5 to 8.0% by mass, more preferably 0.7 to 5.0% by mass.

If the content is less than 0.1% by mass, the impact strength of the obtained molded body is insufficient. Moreover, when the content is 10% by mass or less, it is preferable in terms of economy.

Here, the content and chain length of the polyorganosiloxane block portion in the resin composition are calculated by nuclear magnetic resonance (NMR) measurement.

Further, in the polycarbonate resin composition of the present invention, the content of the above-mentioned butadiene-derived structural unit in the total resin composition is from 3 to 10% by mass. When the content of the structural unit derived from butadiene is less than 3% by mass, the impact resistance of the molded body is insufficient, and when it exceeds 10% by mass, the fluidity and the flame retardancy are lowered. In view of the above, the polycarbonate resin composition of the present invention preferably has a content of the above butadiene-derived structural unit in the total resin composition of from 3 to 8% by mass, more preferably from 3.5 to 6% by mass. .

Further, in the polycarbonate resin composition of the present invention, the content of the above-mentioned structural unit derived from styrene in the total resin composition is preferably from 5 to 35% by mass, and the content of the structural unit derived from the above acrylonitrile is preferably It is 3 to 10% by mass. When the content of the structural unit derived from styrene is 5% by mass or more, the fluidity is further improved, and when it is 35% by mass or less, the impact resistance of the molded body is easily prevented from being lowered. In addition, when the content of the structural unit derived from acrylonitrile is 3% by mass or more, the compatibility with the component (A) is more favorable, and when it is 10% by mass or less, the impact resistance of the molded article is easily prevented from being lowered.

From the above viewpoints, the polycarbonate resin composition of the present invention is more preferably the above source The content of the structural unit derived from styrene is 7 to 20% by mass, and more preferably 8 to 15% by mass. Further, the content of the structural unit derived from acrylonitrile is more preferably from 3 to 8% by mass, still more preferably from 3 to 6% by mass.

Further, in the polycarbonate resin composition of the present invention, the total content of the styrene-derived structural unit and the acrylonitrile-derived structural unit in the total resin composition is 8 to 45% by mass. When the total content of the styrene-derived structural unit and the content of the acrylonitrile-derived structural unit is 8 to 45% by mass, the fluidity is good, and the impact resistance of the molded article is easily prevented from being lowered.

In view of the above, the polycarbonate resin composition of the present invention preferably has a total content of the structural unit derived from styrene and a content of the structural unit derived from acrylonitrile of 8 to 30% by mass, and further Good is 10~25% by mass.

In the polycarbonate resin composition of the present invention, the total content of the polyorganosiloxane block portion containing the repeating unit represented by the formula (II) and the above-mentioned butadiene-derived structural unit is preferably 3.5~. 15% by mass, more preferably 4.0 to 10% by mass. Both the polyorganosiloxane block portion and the butadiene-derived structural unit improve impact resistance. Therefore, when the total content is 3.5% by mass or more, higher impact resistance can be obtained. In addition, when it is 15% by mass or less, the fluidity can be further suppressed from being lowered.

[Flame retardant (D)]

The polycarbonate resin composition of the present invention preferably further contains a flame retardant as the component (D).

The flame retardant is not particularly limited as long as it has an effect of improving the flammability within the range of the effects of the present invention, and various known flame retardants such as a phosphorus-based flame retardant and a halogen-based flame retardant can be exemplified. Metal salt flame retardant. Among these various known flame retardants, a phosphorus-based flame retardant is preferably used as the component (D) from the viewpoint of imparting high flame retardancy.

Examples of the phosphorus-based flame retardant include a red phosphorus or a phosphate-based flame retardant.

The phosphate-based flame retardant is preferably a halogen-free one, and examples thereof include a phosphate-containing monomer, an oligomer, a polymer, or a mixture thereof. Specific examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl phosphate, and cresyl phosphate. Phenyl ester, diphenyl octyl phosphate, tris(2-ethylhexyl) phosphate, phenyl diphenyl phenyl ester, tris(xylylene) phosphate, tris(isopropylphenyl) phosphate, phosphoric acid Naphthyl ester, bisphenol A diphosphate, hydroquinone diphosphate, resorcinol diphosphate, resorcinol-diphenyl phosphate, trioxybenzene triphosphate, etc., or such substitution Body, condensate, etc. Among them, it is preferred to use a condensed phosphate.

As a commercially available phosphate ester compound which can be preferably used as a phosphate ester-based flame retardant, for example, "TPP" [triphenyl phosphate], "TXP" [phosphoric acid triglyceride) manufactured by Daeba Chemical Industry Co., Ltd. (xylene) ester], "CR733S" [resorcinol bis(diphenyl phosphate)], "CR741" [bisphenol A bis(diphenyl phosphate)], "PX200" [1,3- Phenyl-tetrakis(2,6-dimethylphenyl)phosphate], "PX201L" [1,4-phenylene-tetrakis(2,6-dimethylphenyl)phosphate], "PX202 "[4,4'-Exbiphenyl-tetrakis(2,6-dimethylphenyl)phosphate]].

The phosphate ester-based flame retardant is obtained by a reaction of a dihydric phenol and a monohydric phenol represented by Ar-OH with phosphonium chloride.

These flame retardants may be used alone or in combination of two or more.

The content of the component (D) in the polycarbonate resin composition of the present invention is preferably 10 to 40 parts by mass, more preferably 10 to 30 parts by mass, even more preferably 100 parts by mass to 100 parts by mass of the component (A). 15 to 30 parts by mass. When the content is 10 parts by mass or more, more excellent flame retardancy can be obtained, and the fluidity of the resin composition is further improved. Moreover, when it is 40 mass parts or less, it is easy to maintain impact resistance and heat resistance.

[Other ingredients]

In the polycarbonate resin composition of the present invention, the present invention can be not significantly impaired The degree of effect appropriately contains other ingredients.

Examples of other components include additives such as an antioxidant, an ultraviolet absorber, a release agent, a flame retardant auxiliary, an inorganic filler, and a colorant (dye, pigment).

Examples of the antioxidant include a phosphorus-based antioxidant, a sulfur-based antioxidant, and a phenol-based antioxidant.

The phosphorus-based antioxidant is not particularly limited. Typical examples thereof include tris(nonylphenyl)phosphite, 2-ethylhexyl phosphite diphenyl ester, and examples thereof include trialkyl phosphite, tricycloalkyl phosphite, and triaryl phosphite. A base ester, a trialkyl phosphate, a tricycloalkyl phosphate, a triaryl phosphate, or the like. Among them, a triaryl phosphite and a triaryl phosphate can be preferably used.

The sulfur-based antioxidant is not particularly limited, and is preferably pentaerythritol tetrakis(3-laurylthiopropionate) or tetrakis[methylene-3-(dodecylthio)propionate]methane.

The phenolic antioxidant is not particularly limited, and a hindered phenol system is preferably used. Among them, preferred is octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4) -hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5- Trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene and the like.

In the case of using an antioxidant, one type may be used alone or two or more types may be used in combination. As the antioxidant, a phosphorus-based antioxidant is preferably used, and a phosphorus-based antioxidant or a phosphorus-based antioxidant and a sulfur-based antioxidant and/or a phenol-based antioxidant are preferably used in combination.

The amount of the antioxidant is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 3 parts by mass, even more preferably 0.01 to 1 part by mass, per 100 parts by mass of the component (A). When the amount of the antioxidant is within the above range, discoloration or molecular weight reduction during molding of the resin composition can be sufficiently prevented, and the antioxidant effect can be enhanced.

As the ultraviolet absorber, a benzophenone type, a benzotriazole type, or a hydroxyphenyl group can be used. An ultraviolet absorber such as a cyclic imine ester or a cyanoacrylate. The ultraviolet absorber may be used singly or in combination of two or more. As the ultraviolet absorber, at least one selected from the group consisting of a benzophenone-based ultraviolet absorber and a benzotriazole-based ultraviolet absorber is preferably used, and a benzotriazole-based ultraviolet absorber is more preferably used.

Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-octyloxydiphenyl. Methyl ketone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonylbenzophenone, 2-hydroxy-4-methoxy-5-sulfonate Mercapto trihydrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'- Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfonic acid sodium benzophenone, bis(5-benzene Mercapto-4-hydroxy-2-methylphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'- Carboxybenzophenone and the like.

Examples of the benzotriazole-based ultraviolet absorber include 2-(2-hydroxy-5-methylphenyl)benzotriazole and 2-(2-hydroxy-5-th-octylphenyl)benzene. Triazole, 2-(2-hydroxy-3,5-diisopropylphenylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl )-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2- Phenyl], 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)-5 -Chlorobenzotriazole, 2-(2-hydroxy-3,5-di-t-pentylphenyl)benzotriazole, 2-(2-hydroxy-5-th-octylphenyl)benzotriene Oxazole, 2-(2-hydroxy-5-t-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)benzotriazole, 2,2'-methylene Bis(4-isopropylphenyl-6-benzotriazolephenyl), 2,2'-p-phenylene bis(1,3-benzoate) 4-keto), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, And a copolymer of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer or 2-( 2'-hydroxy-5-propenyloxyethylphenyl)-2H-benzotriazole and a copolymer of a vinyl monomer copolymerizable with the monomer, etc., having 2-hydroxyphenyl-2H- a polymer of a benzotriazole skeleton or the like.

The amount of the ultraviolet absorber to be added to the polycarbonate resin composition of the present invention is preferably 0.001 to 1 part by mass, more preferably 0.005 to 0.7 part by mass, more preferably 0.005 to 0.7 part by mass, based on 100 parts by mass of the component (A). 0.01 to 0.5 parts by mass. When the amount of the ultraviolet absorber is 0.001 parts by mass or more, coloring such as yellowing of the molded body can be sufficiently suppressed. Moreover, when it is 1 part by mass or less, it is economically preferable, and there is no case where mold contamination occurs during molding.

As the mold release agent, a fatty acid ester, a polyolefin wax, a fluorine oil, a paraffin wax or the like can be used. Among them, preferred are fatty acid esters, for example, stearic acid monoglyceride, stearic acid diglyceride, stearic acid monosorbitan ester, behenic acid monoglyceride, pentaerythritol monostearate, Partial esters such as pentaerythritol distearate, propylene glycol monostearate, sorbitan monostearate, glyceryl monostearate, or pentaerythritol tetrastearate. These may be used alone or in combination of two or more.

The amount of the release agent to be added to the polycarbonate resin composition of the present invention is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, even more preferably 100 parts by mass based on 100 parts by mass of the component (A). 0.2 to 2 parts by mass.

The flame retardant aid is preferably used in combination with the flame retardant (D), and a polytetrafluoroethylene (PTFE) or a ruthenium oxide compound can be used. Among them, PTFE is preferably used, and it is preferred to use PTFE having fibril forming ability. Further, it is also preferred to use a mixed powder comprising PTFE particles and organic polymer particles.

Specific examples of the monomer for producing the organic polymer particles include a styrene monomer, a (meth)acrylic acid alkyl ester monomer, a vinyl cyanide monomer, and a vinyl ether monomer. a vinyl carboxylate monomer; an olefin monomer; a diene monomer. It is especially preferred to use an alkyl (meth)acrylate monomer. In addition, the alkyl (meth)acrylate system means a monomer of both an alkyl acrylate type and an alkyl methacrylate type.

Organic polymer particles can be obtained by polymerizing the monomers. These monomers may be used alone or in combination of two or more. As the organic polymer particles, it is preferable to contain A particle of a (meth)acrylic acid alkyl ester copolymer.

The amount of the flame retardant auxiliary is preferably 0.1 to 2 parts by mass, more preferably 0.3 to 1.5 parts by mass, per 100 parts by mass of the component (A).

Examples of the inorganic filler include talc, mica, kaolin, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, glass fiber, carbon fiber, and potassium titanate fiber. Among them, a plate-like talc, mica, or the like, or a fibrous filler such as glass fiber or carbon fiber is preferable. The flame retardancy or dimensional stability can be further improved by blending the inorganic filler.

These may be used alone or in combination of two or more.

The amount of the inorganic filler to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the component (A). When the amount is 0.1 part by mass or more, the effect of improving the flame retardancy or the dimensional stability can be sufficiently obtained. When the amount is 10 parts by mass or less, the fluidity and the impact resistance are easily maintained.

Examples of the colorant include an anthraquinone dye, a coumarin dye, a thioindigo dye, an anthraquinone dye, and 9-oxygen sulfur. A dye, a ferrocyanide, an anthraquinone dye, a quinoline dye, a dye of a phthalocyanine dye, or the like.

<Physical properties of polycarbonate resin composition>

The polycarbonate resin composition of the present invention is excellent in fluidity. Specifically, the MFR which is measured at a temperature of 260 ° C and a load of 2.16 kg is usually 10 g/10 min or more, preferably 15 g/10 min or more, more preferably 20 g/10 min or more.

The upper limit of the MFR is not particularly limited and is usually 100 g/10 minutes or less. The MFR can be determined in accordance with ASTM D1238.

Further, as another index indicating the fluidity of the resin composition, there is a Q value or a spiral flow length (SFL). The polycarbonate resin composition of the present invention has a Q value of usually 0.10 mL/sec or more, preferably 0.20 mL/sec or more, more preferably 0.25 mL/sec or more, measured at a temperature of 260 ° C and a load of 100 kg. Things. The upper limit of the Q value is not particularly limited, usually It becomes 1.0 mL/sec or less.

Further, in the polycarbonate resin composition of the present invention, the flow length (SFL) at the time of molding at a pressure of 125 MPa is usually 35 cm or more by using a spiral flow mold having a cylinder temperature of 240 ° C, a mold temperature of 40 ° C, and a thickness of 2.0 mm. Preferably, it is 42 cm or more, More preferably, it is 45 cm or more. Specifically, the Q value and the SFL can be measured by the method described in the examples.

As described above, since the polycarbonate resin composition of the present invention has high fluidity, for example, a thin-walled and large-sized molded body can be formed.

The temperature on summer polycarbonate resin composition of the present invention the ratio of the impact strength to the molded article having a thickness of 4mm at the measured value is generally 23 ℃ 15kJ / m ² or more, preferably 20kJ / m ² or more, More preferably, it is 30 kJ/m ² or more. Charpy impact strength A test piece having a notch was prepared from a molded body having a thickness of 4 mm, and was measured at a temperature of 23 ° C according to ISO 179. Specifically, it can be measured by the method described in the examples.

The polycarbonate resin composition of the present invention preferably has a flame retardancy based on UL94 (Underwriters Laboratory ‧ Subject 94) and a 5V grade in a molded body having a thickness of 1.5 mm. Further, the polycarbonate resin composition of the present invention preferably has a flame retardancy based on the UL94 standard and satisfies the V-1 grade in a molded body having a thickness of 1.2 mm. The flame retardancy can be measured by a vertical burning test according to the UL94 standard, and specifically, it can be measured by the method described in the examples.

The polycarbonate resin composition of the present invention is excellent in chemical resistance. The term "excellent chemical resistance" means having a low resistance to a decrease in physical properties of a polycarbonate resin composition caused by contact with a chemical such as a solvent, an emulsifier, a preservative or an oil. Specifically, in the three-point bending test method, after applying a predetermined chemical after applying a strain of 1.0% and leaving it for 200 hours, no change in appearance such as cracks, cracks, and cracks was observed.

<Method for Producing Polycarbonate Resin Composition>

Next, a method for producing the polycarbonate resin composition of the present invention will be described.

The polycarbonate resin composition of the present invention is obtained by blending the above components (A), (B) and (C), and optionally using the component (D), and further general components, and kneading them.

The mixing and kneading at this time can be pre-mixed by using a commonly used machine such as a belt mixer, a drum, etc., and using a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw It is carried out by a method such as an extruder, a multi-screw extruder, or a two-way kneader.

The heating temperature during the kneading is usually appropriately selected in the range of 240 to 300 °C.

Further, the components other than the polycarbonate resin (A) may be melt-kneaded with the polycarbonate resin (A) in advance, that is, may be added as a master batch.

[formed body]

The molding system of the present invention comprises the polycarbonate resin composition of the present invention.

The molding system of the present invention is produced by a composition obtained by melt-kneading using the above melt-kneading molding machine or a pellet obtained from the composition, by injection molding, injection compression molding, extrusion molding, and blow molding. The polycarbonate resin composition of the present invention is obtained by molding, a press molding method, a vacuum molding method, a foam molding method, and the like.

It is particularly preferable to produce a pellet-shaped molding material by the above-described melt-kneading method, and then use the pellets, and use injection molding and injection compression molding to obtain a molded body.

Further, as the injection molding method, a gas injection molding method for preventing the appearance of dents or for weight reduction may be employed.

<Physical properties of the molded body>

With respect to the molded body of the polycarbonate resin composition of the present invention obtained in the above manner, a test piece having a thickness of 4 mm is used, and the bending strength measured at 23 ° C according to ISO 178 is usually For 85~95MPa, the flexural modulus is usually 2,000~3,000MPa.

Further, specifically, the above characteristic values were measured by the methods described in the examples.

The molded article of the present invention is also excellent in heat resistance.

The polycarbonate resin composition of the present invention and a molded body comprising the same can be preferably used for an automobile part (e.g., exterior, interior, instrument panel, etc.), an electronic device or an outer casing of an information device, and the like.

[Examples]

The invention is illustrated in more detail by way of examples, but the invention is not limited thereto.

(1) Polydimethylsiloxane (PDMS) chain length and content

It was calculated by NMR measurement based on the integrated value ratio of the methyl group of polydimethylsiloxane.

<Quantitative method of chain length of polydimethyl methoxy oxane>

1H-NMR measurement conditions

NMR device: ECA500 manufactured by JEOL RESONANCE Co., Ltd.

Probe: 50TH5AT/FG2

Observation range: -5~15ppm

Observation Center: 5ppm

Pulse repetition time: 9 seconds

Pulse width: 45°

NMR sample tube: 5

Sample size: 30~40mg

Solvent: chloroform

Measuring temperature: room temperature

Cumulative number: 256 times

Allyl phenol end polydimethyl oxane

A: The integral value of the methyl group of the dimethyloxane moiety observed near δ-0.02~0.5

B: integral value of methylene group of allylphenol observed in the vicinity of δ2.50~2.75

Chain length of polydimethyl methoxy alkane = (A / 6) / (B / 4)

The case of eugenol end polydimethyl oxane

A: The integral value of the methyl group of the dimethyloxane moiety observed near δ-0.02~0.5

B: integral value of methylene group of eugenol observed in the vicinity of δ 2.40~2.70

Chain length of polydimethyl methoxy alkane = (A / 6) / (B / 4)

<Quantification method of the content of polydimethylsiloxane oxime block fraction in PC-PDMS>

Example) Method for quantifying the amount of polydimethyl methoxy alkane copolymerized in a tertiary butyl phenol (PTBP) terminal polycarbonate by copolymerizing allyl phenol terminal polydimethyl methoxy alkane

NMR device: ECA-500 manufactured by JEOL RESONANCE Co., Ltd.

Probe: with TH5 5 NMR sample tube corresponding

Observation range: -5~15ppm

Observation Center: 5ppm

Pulse repetition time: 9 seconds

Pulse width: 45°

Cumulative number: 256 times

NMR sample tube: 5

Solvent: chloroform

Measuring temperature: room temperature

A: The integral value of the methyl group of the BPA portion observed near δ1.5~1.9

B: the integral of the methyl group of the dimethyloxane observed in the vicinity of δ-0.02~0.3 value

C: integral value of the butyl group of the third butyl group observed in the vicinity of δ1.2~1.4

a=A/6

b=B/6

c=C/9

T=a+b+c

f=a/T×100

g=b/T×100

h=c/T×100

TW=f×254+g×74.1+h×149

PDMS (wt%) = g × 74.1/TW × 100

(2) Viscosity average molecular weight of polycarbonate-polyorganosiloxane copolymer and polycarbonate resin composition

The viscosity average molecular weight (Mv) is determined by using a Ubbelohde viscometer to determine the viscosity of a dichloromethane solution (concentration unit: g/L) at 20 ° C, and the ultimate viscosity [η] is determined according to the following formula (Schnell type). ) and calculate.

[η]=1.23×10 ^-5 ×Mv ^0.83

Preparation Example 1

<Polymer oligomer manufacturing>

In a 5.6 mass% aqueous sodium hydroxide solution, 2000 ppm of sodium disulfite was added to the bisphenol A (BPA) dissolved thereafter. BPA was dissolved in such a manner that the BPA concentration became 13.5% by mass to prepare a BPA aqueous sodium hydroxide solution. A tubular reactor having an inner diameter of 6 mm and a tube length of 30 m was continuously passed through a flow rate of 40 L/hr of a sodium hydroxide aqueous solution of BPA and a flow rate of 15 L/hr of dichloromethane at a flow rate of 4.0 kg/hr of phosgene. The tubular reactor has a sleeve portion in which the temperature of the reaction liquid is maintained below 40 ° C via cooling water. The reaction liquid flowing out of the tubular reactor is continuously introduced into the internal volume 40L with the swept-back blade A trough-type reactor in which a BPA sodium hydroxide aqueous solution is 2.8 L/hr, a 25 mass% sodium hydroxide aqueous solution is 0.07 L/hr, water is 17 L/hr, and a 1 mass% triethylamine aqueous solution is 0.64 L/ The reaction was carried out by adding hr. The aqueous phase was separated and removed by continuously withdrawing the reaction liquid overflowed from the tank type reactor and standing, and a dichloromethane phase was collected.

The polycarbonate oligomer obtained in this manner had a concentration of 329 g/L and a chloroformate group concentration of 0.74 mol/L.

Manufacturing example 1

<Manufacture of Polycarbonate-Polydimethylsiloxane Copolymer (PC-PDMS Copolymer 1)>

Into a 50 L tank reactor equipped with a separator, a slurry type stirring blade and a cooling jacket, 15 L of the polycarbonate oligomer solution prepared in the above Preparation Example 1, 9.0 L of dichloromethane, and polydimethyl hydrazine were added. 384 g of o-allylphenol end-modified polydimethyloxane (PDMS) and 8.8 mL of triethylamine having an average chain length n of 90, and a solution of 6.4% by mass aqueous sodium hydroxide 1389 g was added thereto with stirring. The reaction of the polycarbonate oligomer with allyl phenol end-modified PDMS was carried out for 10 minutes.

To the polymerization solution, a dichloromethane solution of p-butylphenol (PTBP) (a solution obtained by dissolving 137 PTBP in 2.0 L of dichloromethane) and a sodium hydroxide aqueous solution of bisphenol A (making bisphenol A 1012 g) were added to the polymerization solution. The solution was dissolved in an aqueous solution obtained by dissolving 577 g of sodium hydroxide and 2.0 g of sodium disulfite in 8.4 L of water, and carrying out a polymerization reaction for 50 minutes.

For dilution, 10 L of dichloromethane was added, and after stirring for 10 minutes, it was separated into an organic phase containing a polycarbonate-polydimethylsiloxane (PC-PDMS copolymer) and an excess of bisphenol A and hydrogen. The aqueous phase of sodium oxide is separated from the organic phase.

With respect to the thus obtained dichloromethane solution of the PC-PDMS copolymer, the solution was sequentially washed with 15% by volume of a 0.03 mol/L sodium hydroxide aqueous solution and 0.2 mol/L hydrochloric acid, followed by repeated washing with pure water until washing. The conductivity in the subsequent aqueous phase is 0.01 μS/m or less.

Concentrating the dichloromethane solution of the PC-PDMS copolymer obtained by washing, The sheet was pulverized, and the obtained sheet was dried at 120 ° C under reduced pressure to prepare PC-PDMS copolymer 1.

The content of the PDMS block portion obtained by nuclear magnetic resonance (NMR) of the obtained PC-PDMS copolymer 1 was 6.0% by mass, the viscosity value was 47.5, and the viscosity average molecular weight Mv was 17,700.

Manufacturing Example 2

<Manufacture of Polycarbonate-Polydimethyloxane Copolymer (PC-PDMS Copolymer 2)>

In the same manner as in Production Example 1, a PC-PDMS copolymer was produced in the same manner as in Production Example 1, except that the polydimethylsiloxane was used for the terminally modified PDMS having an average chain length n of 40. 2.

The content of the PDMS block portion obtained by NMR of the obtained PC-PDMS copolymer 2 was 6.0% by mass, the viscosity value was 47.5, and the viscosity average molecular weight Mv was 17,700.

The average chain length n of PDMS of the allyl phenol end-modified polydimethyloxane used in the above production example, the amount of PDMS used, and the amount of p-tert-butylphenol (PTBP) used, obtained The content, viscosity value, and viscosity average molecular weight Mv of the PDMS block portion of the polycarbonate-polydimethylsiloxane copolymer are shown in Table 1. Further, the viscosity value measured in the production example of the present invention is a value measured in accordance with ISO 1628-4 (1999).

[Performance evaluation]

<liquidity evaluation>

(MFR)

The MFR at a temperature of 260 ° C and a load of 2.16 kg was measured in accordance with ASTM D1238.

(Q value)

According to JIS K7210, the Q value at a temperature of 260 ° C and a load of 100 kg was measured by an overhead rheometer.

(SFL value)

Using a spiral flow mold having a cylinder temperature of 240 ° C, a mold temperature of 40 ° C, and a thickness of 2.0 mm, the pellets obtained in each of the examples were formed at a pressure setting of 125 MPa, and the flow length (cm) at this time was measured.

<Evaluation of impact resistance>

(Charpy impact strength)

A test piece having a thickness of 4 mm obtained from each of the examples was prepared, and a test piece having a notch was prepared, and the Charpy impact strength was measured at a temperature of 23 ° C according to ISO 179. The larger the value, the better the impact resistance.

<Mechanical characteristics evaluation>

(Bending test)

The test piece having a thickness of 4 mm obtained in each example was used, and the bending strength and the flexural modulus were measured in accordance with ISO 178 at a temperature of 23 ° C and a bending speed of 2 mm / min. The larger the value, the better the bending characteristics.

<heat resistance evaluation>

(load deformation temperature)

Using a test piece having a thickness of 4 mm obtained in each example, the load deformation temperature (HDT) was measured at a load of 1.8 MPa in accordance with the measurement method of ISO 75-1 and 2. The higher the load deformation temperature, the better the heat resistance.

<Flame retardancy evaluation>

(UL94 flammability)

For the test pieces having a thickness of 1.5 mm obtained in each example, a 5 V burning test (n=5) was carried out in accordance with the UL94 vertical flame retardant test (US Underwriters Laboratories ‧ Subject 94), and the total of the five burning times (seconds) was determined. In the flame retardancy evaluation, those who satisfy the 5V level are referred to as "5V", and those who do not satisfy the 5V level are referred to as "5V-OUT".

For the test piece having a thickness of 1.2 mm obtained in each example, a burning test (n=5) was carried out in accordance with the UL94 vertical flame retardant test (US Underwriters Laboratories ‧ Subject 94), and the total of the five burning times (seconds) was determined. In the flame retardancy evaluation, those who satisfy the V-0 rating are referred to as "V-0", those who satisfy the V-1 rating are referred to as "V-1", and those who do not satisfy are referred to as "V-OUT".

<Chemical resistance evaluation>

(three-point bending test)

For the ISO dumbbell test piece having a thickness of 4.0 mm obtained in each example, a strain of 1.0% was applied by a three-point bending test, and the prescribed chemical was applied to the portion to which the tensile stress was applied, and left at 23 ° C for 200 hours. To confirm the appearance change. The test was carried out with the number of samples (n) being 3, and evaluation was performed according to the following criteria.

Regarding the three samples, those who have no appearance change are referred to as "A", those who have cracks are referred to as "B", and those who have cracks or cracks are referred to as "C".

Furthermore, the following two chemicals are used.

"telluss 68" (Shell telluss S2 M 68 "Hydraulic Oil", manufactured by Showa-Shell Petroleum Co., Ltd.)

"EP-1" (manufactured by NTN Co., Ltd.)

Examples 1 to 5 and Comparative Examples 1 to 10

Mix the ingredients in the ratio shown in Table 2, using 50mm with venting holes The uniaxial extruder was granulated at a resin temperature of 280 ° C to obtain granules containing a polycarbonate resin composition.

Injection molding machine (Model: "IS100EN", manufactured by Toshiba Machine Co., Ltd. The pellet obtained by the above method was injection-molded under the molding conditions of a cylinder temperature of 240 ° C and a mold temperature of 40 ° C to obtain a test piece. The above performance evaluation was performed using the obtained test piece.

The details of the components shown in Table 2 used in the examples and comparative examples are as follows.

<Polycarbonate-polyorganosiloxane copolymer (A-1)>

PC-PDMS copolymer 1 (polycarbonate-polydimethylsiloxane copolymer described in Production Example 1)

PC-PDMS copolymer 2 (polycarbonate-polydimethylsiloxane copolymer described in Production Example 2)

<Aromatic polycarbonate resin (A-2)>

"Tarflon FN2200" (bisphenol A polycarbonate, manufactured by Idemitsu Kosan Co., Ltd., viscosity value 56.1, viscosity average molecular weight Mv = 21,500)

"Tarflon FN1900" (bisphenol A polycarbonate, manufactured by Idemitsu Kosan Co., Ltd., viscosity value 51.0, viscosity average molecular weight Mv = 19,200)

"Tarflon FN1700" (bisphenol A polycarbonate, manufactured by Idemitsu Kosan Co., Ltd., viscosity 47.5, viscosity average molecular weight Mv = 17,700)

<Acrylonitrile-butadiene-styrene terpolymer (B-1)>

"Kralastic SXH-330" (Acrylonitrile-butadiene-styrene terpolymer (ABS), manufactured by Japan A&L Co., Ltd., content of structural units derived from butadiene: 12% by mass)

"Santac AT05" (Acrylonitrile-butadiene-styrene terpolymer (ABS), manufactured by Japan A&L Co., Ltd., content of structural units derived from butadiene: 14% by mass)

"HR181" (Acrylonitrile-butadiene-styrene terpolymer (ABS), manufactured by KUMHO PETROCHEMICAL Co., Ltd., content of structural units derived from butadiene: 60% by mass)

<Acrylonitrile-styrene binary copolymer (B-2)>

"S101N" (acrylonitrile-styrene binary copolymer (AS), manufactured by UMG ABS Co., Ltd., MVR [temperature 200 ° C, load 10 kgf]: 95 cm ³ / 10 minutes)

<Copolymer (C)>

"M-701" (Kaneace M-701 (MBS), average particle size 500nm, manufactured by Kaneka Co., Ltd.)

"M-711" (Kaneace M-711 (MBS), average particle size 200nm, manufactured by Kaneka Co., Ltd.)

"Metablen C223A" (methyl methacrylate-butadiene-styrene terpolymer (MBS), average particle size 260 nm, manufactured by Mitsubishi Rayon Co., Ltd.)

"Paraloid EXL2690" (methyl methacrylate-butadiene binary copolymer (MB), average particle diameter 200 nm, manufactured by Dow Chemical)

"Paraloid EXL2603" (methyl methacrylate-butadiene binary copolymer (MB), average particle diameter 200 nm, manufactured by Dow Chemical)

<Flame retardant (D)>

"CR-741" (aromatic condensed phosphate ester flame retardant, manufactured by Daiba Chemical Industry Co., Ltd.)

<Flame retardant additive>

"Fluon AD939E" (PTFE aqueous dispersion, manufactured by Asahi Glass Co., Ltd.)

The various evaluation results are shown in Table 2.

According to Table 2, the polycarbonate resin composition of the present invention is excellent in fluidity, flame retardancy, impact resistance, and chemical resistance, and is also excellent in mechanical properties and heat resistance.

[Industrial availability]

According to the present invention, it is possible to provide a polycarbonate resin composition which is excellent in fluidity, flame retardancy, and chemical resistance and which can obtain a molded body having high impact strength. Since the resin composition can form a thin-walled and large-sized molded body, it can be preferably used for an automobile part (for example, an exterior, an interior, an instrument panel, etc.), an electronic device, or an outer casing of an information device.

Claims (15)

A polycarbonate resin composition comprising: a polycarbonate resin (A) comprising a polycarbonate-polyorganosiloxane copolymer (A-1), the polycarbonate-polyorganosiloxane copolymer (A-1) a polycarbonate block having a repeating unit represented by the following formula (I) and a polyorganooxy oxyalkylene block comprising a repeating unit represented by the following formula (II); (B) having structural units derived from acrylonitrile and styrene and having no structural unit derived from methyl methacrylate; and copolymer (C) having derived from butadiene and methyl methacrylate And the content of the polyorganosiloxane block portion in the total resin composition is 0.1 to 10% by mass, and the above-mentioned acrylonitrile-derived structural unit and total resin composition in the total resin composition The content of the above-mentioned structural unit derived from styrene is 8 to 45% by mass, and the content of the above-mentioned butadiene-derived structural unit in the total resin composition is 3 to 10% by mass, and the above polycarbonate resin ( A) has a viscosity average molecular weight (Mv) of 20,000 to 25,000. [wherein R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; and X represents a single bond, an alkylene group having 1 to 8 carbon atoms, An alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a fluorenyldiyl group, an arylalkyl group having 7 to 15 carbon atoms, and a carbon number of 7 ~15 arylalkylene, -S-, -SO-, -SO ₂ -, -O- or -CO-; R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 6 The alkyl group, the alkoxy group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms; a and b each independently represent an integer of 0 to 4]. The polycarbonate resin composition of claim 1, wherein the content of the polyorganosiloxane component in the polycarbonate resin (A) is 0.1 to 15% by mass. The polycarbonate resin composition of claim 1 or 2, wherein the polyorganosiloxane mixture in the polycarbonate-polyorganosiloxane copolymer (A-1) has a chain length of from 30 to 500. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the above copolymer (B) comprises an acrylonitrile-butadiene-styrene terpolymer (B-1). The polycarbonate resin composition according to any one of claims 1 to 4, wherein the above copolymer (B) comprises an acrylonitrile-styrene binary copolymer (B-2). The polycarbonate resin composition according to any one of claims 1 to 5, wherein the copolymer (C) comprises a methyl methacrylate-butadiene-styrene terpolymer and methyl methacrylate. At least one of the group consisting of butadiene binary copolymers. The polycarbonate resin composition according to any one of claims 1 to 6, wherein the above copolymer (C) is a methyl methacrylate-butadiene binary copolymer. The polycarbonate resin composition according to any one of claims 1 to 7, wherein the copolymer (C) has an average particle diameter of from 100 nm to 300 nm. The polycarbonate resin composition according to any one of claims 5 to 8, wherein the above acrylonitrile-butadiene-styrene terpolymer (B- is 100 parts by mass relative to the above polycarbonate resin (A). 1) The content is 8 to 100 parts by mass, the content of the acrylonitrile-styrene binary copolymer (B-2) is 20 parts by mass or less, and the content of the copolymer (C) is 1 to 8 parts by mass. The polycarbonate resin composition according to any one of claims 1 to 9, which further comprises a hindrance Fuel (D). The polycarbonate resin composition of claim 10, wherein the flame retardant (D) is a phosphorus-based flame retardant. The polycarbonate resin composition of claim 11, wherein the phosphorus-based flame retardant is a condensed phosphate. The polycarbonate resin composition according to any one of claims 1 to 9, which further comprises a flame retardant (D) which is a phosphorus-based flame retardant as a condensed phosphate ester, and the above copolymerization The substance (C) is a methyl methacrylate-butadiene binary copolymer. The polycarbonate resin composition according to any one of claims 10 to 13, wherein the flame retardant (D) is contained in an amount of 10 to 40 parts by mass based on 100 parts by mass of the polycarbonate resin (A). A molded body comprising the polycarbonate resin composition according to any one of claims 1 to 14.